Synergistic stabilizer mixture

ABSTRACT

Stabilizer mixture comprising, for example, a compound of the formula ##STR1## and, for example, a compound of the formula ##STR2##

This Application is a Divisional 08/680,077 filed Jul. 15, 1996, nowU.S. Pat. No. 5,919,399.

The present invention relates to a stabilizer system comprising twospecific polyalkylpiperidine derivatives, to the use of this stabilizersystem for stabilizing organic material, and to the organic materialprotected against thermal, oxidative or light-induced degradation bymeans of the stabilizer system mentioned.

U.S. Pat. No. 4,692,486, U.S. Pat. No. 4,863,981, U.S. Pat. No.4,957,953, U.S. Pat. No. 5,021,485, U.S. Pat. No. 5,439,959, WO-A-92/12201, WO-A-94/22 946, EP-A-449 685, EP-A-632 092, GB-A-2 267 499 andResearch Disclosure 34 549 (January 1993) describe a number ofstabilizer mixtures which comprise two polyalkylpiperidine derivatives.

The present invention relates to a stabilizer mixture comprising atleast two different compounds from the group consisting of componentsa), b), c), d), e), f), g), h), i), j), k) and l), where

component a) is at least one compound of the formula I ##STR3## in whichR₁ is hydrogen, C₁ -C₁₈ alkyl, C₅ -C₁₂ cycloalkyl or C₁ -C₄alkyl-substituted C₅ -C₁₂ cycloalkyl,

n₁ is 1, 2 or 4,

if n₁ is 1, R₂ is C₁ -C₂₅ alkyl,

if n₁ is 2, R₂ is C₁ -C₁₄ alkylene and

if n₁ is 4, R₂ is C₄ -C₁₀ alkanetetrayl;

component b) is at least one compound of the formula II ##STR4## inwhich R₃ and R₇ independently of one another are hydrogen or C₁ -C₁₂alkyl,

R₄, R₅ and R₆ independently of one another are C₂ -C₁₀ alkylene, and

X₁, X₂, X₃, X₄, X₅, X₆, X₇ and X8 independently of one another are agroup of the formula ##STR5## in which R₈ is hydrogen, C₁ -C₁₂ alkyl, C₅-C₁₂ cycloalkyl, C₁ -C₄ alkyl-substituted C₅ -C₁₂ cycloalkyl, phenyl,--OH-- and/or C₁ -C₁₀ alkyl-substituted phenyl, C₇ -C₉ phenylalkyl, C₇-C₉ phenylalkyl which is substituted on the phenyl radical by --OHand/or C₁ -C₁₀ alkyl; or a group of the formula IV, ##STR6## and R₉ andR₁₀ independently of one another are as defined for R₁ ;

component c) is at least one compound of the formula V, ##STR7## inwhich X₉, X₁₀ and X₁₁, independently of one another are a group of theformula III;

component d) is at least one compound of the formula VI, ##STR8## inwhich R₁₁, R₁₃, R₁₄ and R₁₅ independently of one another are hydrogen,C₁ -C₁₂ alkyl, C₅ -C₁₂ cycloalkyl, C₁ -C₄ alkyl-substituted C₅ -C₁₂cycloalkyl, phenyl, --OH-- and/or C₁ -C₁₀ alkyl-substituted phenyl, C₇-C₉ phenylalkyl, C₇ -C₉ phenylalkyl which is substituted on the phenylradical by --OH and/or C₁ -C₁₀ alkyl; or a group of the formula IV,

R₁₂ is C₂ -C₁₈ alkylene, C₅ -C₇ cycloalkylene or C₁ -C₄ alkylenedi(C₅-C₇ cycloalkylene), or the radicals R₁₁, R₁₂ and R₁₃, together with thenitrogen atoms to which they are attached, form a 5- to 10-memberedheterocyclic ring, or

R₁₄ and R₁₅, together with the nitrogen atom to which they are attached,form a 5- to 10-membered heterocyclic ring,

n₂ is a number from 2 to 50, and

at least one of the radicals R₁₁, R₁₃, R₁₄ and R₁₅ is a group of theformula IV;

component e) is at least one compound of the formula VII, ##STR9## inwhich R₁₆ is C₁ -C₁₀ alkyl, C₅ -C₁₂ cycloalkyl, C₁ -C₄ alkyl-substitutedC₅ -C₁₂ cycloalkyl, phenyl or C₁ -C₁₀ alkyl-substituted phenyl,

R₁₇ is C₃ -C₁₀ alkylene,

R₁₈ is as defined for R₁, and

n₃ is a number from 1 to 50;

component f) is a product obtainable by reacting a product, obtained byreaction between a polyamine of the formula VIIIa and cyanuric chloride,with a compound of the formula VIIIb to give a triazine derivative whichcomprises 2,2,6,6-tetramethyl-4-piperidyl groups, and then reacting the2,2,6,6-tetramethyl-4-piperidyl groups present in the triazinederivative to form groups of the formula VIIIc ##STR10## in which n₄ ',n₄ " and n₄ '" independently of one another are a number from 2 to 12,

R₁₉ is hydrogen, C₁ -C₁₂ alkyl, C₅ -C₁₂ cycloalkyl, phenyl or C₇ -C₉phenylalkyl, and

R₂₀ is as defined for R₁ ;

component g) is at least one compound of the formula IX, ##STR11## inwhich R₂₁ and R₂₆ independently of one another are a direct bond or agroup --N(Y₁)--CO--Y₂ --CO--N(Y₃)--,

Y₁ and Y₃ independently of one another are hydrogen, C₁ -C₈ alkyl, C₅-C₁₂ cycloalkyl, phenyl, C₇ -C₉ phenylalkyl or a group of the formulaIV,

Y₂ is a direct bond or C₁ -C₄ alkylene,

R₂₂ is as defined for R₁,

R₂₃, R₂₄, R₂₇ and R₂₈ independently of one another are hydrogen, C₁ -C₃₀alkyl, C₅ -C₁₂ cycloalkyl or phenyl,

R₂₅ is hydrogen, C₁ -C₃₀ alkyl, C₅ -C₁₂ cycloalkyl, phenyl, C₇ -C₉phenylalkyl or a group of the formula IV, and

n₅ is a number from 1 to 50;

component h) is at least one compound of the formula X ##STR12## inwhich R₂₉ is C₁ -C₂₄ alkyl and

R₃₀ is as defined for R₁ ;

component i) is at least one compound of the formula XI, ##STR13## inwhich R₃₁ is as defined for R₁ and

n₆ is a number from 2 to 50;

component j) is at least one compound of the formula XII ##STR14## inwhich R₃₂ and R₃₃ together form C₂ -C₁₄ alkylene,

R₃₄ is hydrogen or a group --Z₁ --COO--Z₂, Z₁ is C₂ -C₁₄ alkylene and Z₂is C₁ -C₂₄ alkyl, and

R₃₅ is as defined for R₁ ;

component k) is at least one compound of the formula XIII ##STR15## inwhich R₃₆, R₃₇, R₃₈, R₃₉ and R₄₀ independently of one another are adirect bond or C₁ -C₁₀ alkylene,

R₄₁ is as defined for R₁, and

n₇ is a number from 1 to 50;

component 1) is at least one compound of the formula XIV, ##STR16## inwhich X₁₂, X₁₃ and X₁₄ independently of one another are a group of theformula XV, ##STR17## in which A is a group of the formula III.

Examples of alkyl having up to 30 carbon atoms are methyl, ethyl,propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl,2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl,n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl,1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl,1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl,1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethyl-hexyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl,docosyl and triacontyl. One of the preferred meanings of R₂₃ and R₂₇ isC₁ -C₂₅ alkyl, especially C₁₅ -C₂₅ alkyl, for example hexadecyl and C₁₈-C₂₂ alkyl. One of the preferred meanings of R₂₅ is C_(1-C) ₂₅ alkyl,especially octadecyl. One of the preferred meanings of R₈ and R₁₉ is C₁-C₄ alkyl, especially n-butyl.

Examples of C₅ -C₁₂ cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl and cyclododecyl. C₅ -C₈ cycloalkyl, especially cyclohexyl,is preferred.

C₁ -C₄ alkyl-substituted C₅ -C₁₂ cycloalkyl is for examplemethylcyclohexyl or dimethylcyclohexyl.

--OH-- and/or C₁ -C₁₀ alkyl-substituted phenyl is for examplemethylphenyl, dimethylphenyl, trimethylphenyl, tert-butylphenyl or3,5-di-tert-butyl-4-hydroxyphenyl.

Examples of C₇ -C₉ phenylalkyl are benzyl and phenylethyl.

C₇ -C₉ phenylalkyl which is substituted on the phenyl radical by --OHand/or by alkyl having up to 10 carbon atoms is, for example,methylbenzyl, dimethylbenzyl, trimethylbenzyl, tert-butylbenzyl or3,5-di-tert-butyl-4-hydroxybenzyl.

Examples of C₃ -C₆ alkenyl are allyl, 2-methallyl, butenyl, pentenyl andhexenyl. Allyl is preferred. The carbon atom in position 1 is preferablysaturated.

C₁ -C₈ acyl is preferably C₁ -C₈ alkanoyl, C₃ -C₈ alkenoyl or benzoyl.Examples are formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl,octanoyl, benzoyl, acryloyl and crotonoyl.

Examples of alkylene having up to 18 carbon atoms are methylene,ethylene, propylene, trimethylene, tetramethylene, pentamethylene,2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene,octamethylene and decamethylene. R₁₂ is preferably hexamethylene, R₃₆and R₃₈ are preferably methylene, R₃₉ is preferably 2,2-dimethylethyleneand R₄₀ 1,1-dimethylethylene.

An example of C₄ -C₁₀ alkanetetrayl is 1,2,3,4-butanetetrayl.

An example of C₅ -C₇ cycloalkylene is cyclohexylene.

An example of C₁ -C₄ alkylenedi(C₅ -C₇ -cycloalkylene) ismethylenedicyclohexylene.

Where the radicals R₁₁, R₁₂ and R₁₃, together with the nitrogen atoms towhich they are attached, form a 5- to 10-membered heterocyclic ring, theresulting ring is for example ##STR18##

A 6-membered heterocyclic ring is preferred.

Where the radicals R₁₄ and R₁₅, together with the nitrogen atom to whichthey are attached, form a 5- to 10-membered heterocyclic ring, theresulting ring is for example 1-pyrrolidyl, piperidino, morpholino,1-piperazinyl, 4-methyl-1-piperazinyl, 1-hexahydroazepinyl,5,5,7-trimethyl-1-homopiperazinyl or4,5,5,7-tetramethyl-1-homopiperazinyl. Morpholino is particularlypreferred.

One of the preferred meanings of R₂₃ and R₂₇ is phenyl.

Y₂ and R₃₇ are preferably a direct bond.

One of the preferred meanings of Y₁ and Y₃ is hydrogen.

n₂ is preferably 2-25.

n₃ is preferably 1-25, especially 2-20 or 2-10.

n₄ ', n₄ " and n₄ '" are preferably 2-4.

n₅ is preferably 1-25, especially 1-20 or 1-10.

n₆ is preferably 2-25, especially 2-20 or 2-10.

n₇ is preferably 1-25, especially 1-20 or 1-10.

The compounds described as component a) to 1) can be prepared, forexample, by the method indicated below under "Example of a preparationprocess", using the corresponding 2,2,6,6-tetramethylpiperidinederivatives (unsubstituted nitrogen in the2,2,6,6-tetramethyl-4-piperidyl groups) as starting compounds. The2,2,6,6-tetramethylpiperidine derivatives are essentially known (someare commercially available) and can be prepared by known methods, forexample as described in U.S. Pat. No. 3,640,928, U.S. Pat. No.4,108,829, U.S. Pat. No. 3,925,376, U.S. Pat. No. 4,086,204, U.S. Pat.No. 4,331,586, U.S. Pat. No. 5,051,458, U.S. Pat. No. 4,477,615 andChemical Abstracts--CAS No. 136 504-96-6, U.S. Pat. No. 4,857,595,DD-A-262 439 (Derwent 89-122 983/17, Chemical Abstracts 111:58 964u),WO-A-94/12 544 (Derwent 94-177 274/22), U.S. Pat. No. 4,356,307, U.S.Pat. No. 4,340,534, U.S. Pat. No. 4,408,051, U.S. Pat. No. 4,689,416,U.S. Pat. No. 4,110,334, U.S. Pat. No. 4,529,760 and U.S. Pat. No.5,182,390 (Chemical Abstracts--CAS No. 144 923-25-1).

The 2,2,6,6-tetramethylpiperidine derivative starting product belongingto component f) can be prepared in analogy to known methods, for exampleby reacting a polyamine of the formula VIIIa with cyanuric chloride in amolar ratio of from 1:2 to 1:4 in the presence of anhydrous lithiumcarbonate, sodium carbonate or potassium carbonate in an organic solventsuch as 1,2-dichloroethane, toluene, xylene, benzene, dioxane ortert-amyl alcohol at a temperature of from -20° C. to +10° C.,preferably from -10° C. to +10° C., in particular from 0° C. to +10° C.,for from 2 to 8 hours and then reacting the resulting product with a2,2,6,6-tetramethyl-4-piperidylamine of the formula VIIIb. The molarratio of 2,2,6,6-tetramethyl-4-piperidylamine to the polyamine of theformula VIIla which is employed is, for example, from 4:1 to 8:1. Thequantity of 2,2,6,6-tetramethyl-4-piperidylamine can be added in one goor in two or more portions at an interval of a few hours.

The ratio of polyamine of the formula VIIIa to cyanuric chloride to2,2,6,6-tetramethyl-4-piperidylamine of the formula VIIIb is preferablyfrom 1:3:5 to 1:3:6.

The following example indicates a possible method of preparing thepreferred 2,2,6,6-tetramethylpiperidine derivative starting productwhich belongs to component f).

EXAMPLE

23.6 g (0.128 mol) of cyanuric chloride, 7.43 g (0.0426 mol) ofN,N'-bis[3-aminopropyl]ethylenediamine and 18 g (0.13 mol) of anhydrouspotassium carbonate are reacted in 250 ml of 1,2-dichloroethane at 5° C.for 3 hours with stirring. The mixture is heated at room temperature fora further 4 hours. 27.2 g (0.128 mol) ofN-(2,2,6,6-tetramethyl-4-piperidyl)butylamine are added and the mixtureobtained is heated at 60° C. for 2 hours. A further 18 g (0.13 mol) ofanhydrous potassium carbonate are added and the mixture is heated at 60°C. for a further 6 hours. The solvent is distilled off under a slightvacuum (200 mbar) and replaced by xylene. 18.2 g (0.085 mol) ofN-(2,2,6,6-tetramethyl-4-piperidyl)butylamine and 5.2 g (0.13 mol) ofground sodium hydroxide are added and the reaction mixture is heated atreflux for 2 hours, and for a further 12 hours the water produced in thereaction is removed by azeotropic distillation. The mixture is filtered.The solution is washed with water and dried over Na₂ SO₄. The solvent isevaporated off and the residue is dried in vacuo (0.1 mbar) at 120-130°C. The 2,2,6,6-tetramethylpiperidine derivative starting productbelonging to component f) is obtained as a colourless resin.

In general, the 2,2,6,6-tetramethylpiperidine derivative startingproduct belonging to component f) can be represented, for example, by acompound of the formula VIII-1, VIII2 or VIII3. It can also be presentas a mixture of these three compounds. ##STR19##

A preferred meaning of the formula VIII-1 is ##STR20##

A preferred meaning of the formula VIII-2 is ##STR21##

A preferred meaning of the formula VIII-3 is ##STR22##

In the above formulae VIII1 to VIII3, n₄ is preferably from 1 to 20.

Example of a Preparation Process

The compounds described as components a) to 1) can be prepared from theabovementioned 2,2,6,6-tetramethylpiperidine derivative startingproducts in analogy to known methods, for example as disclosed in U.S.Pat. No. 5,204,473, by oxidizing the corresponding2,2,6,6-tetramethylpiperidine derivative with an appropriate peroxycompound, such as hydrogen peroxide or tert-butyl hydroperoxide, in thepresence of a metal carbonyl catalyst or metal oxide catalyst, followedby reduction of the oxyl intermediate formed to give the desiredN-hydroxy derivative, preferably by catalytic hydrogenation.

After this, the O-alkyl derivatives can be synthesized in various ways.For example, the N-hydroxy derivative can be alkylated using sodiumhydride and halogenated hydrocarbons, such as ethyl iodide. N-methoxyvariants can be prepared by thermolysis of a chlorobenzene solution ofthe nitroxyl radical and di-tert-butyl peroxide. The product is formedby a coupling reaction between the nitroxyl radical and the methylradical, which is produced by the β-cleavage of a tert-butoxy radical.

Other N-alkoxy variants can be synthesized by coupling nitroxyl radicalswith hydrocarbon radicals which are formed in the course of the thermaldecomposition of di-tert-butyl peroxide in the presence of hydrocarbonsolvents, such as cyclohexane, toluene and ethylbenzene.

Although these procedures have been described in the context of N-alkoxysubstituents, it is understood that they can be applied equally to allgroups OR₁.

For example, 1-cycloalkyloxy-2,2,6,6-tetramethyl-4-piperidyl derivativescan be prepared by reacting the corresponding2,2,6,6-tetramethyl-4-piperidyl derivative with tert-butyl hydroperoxidein the presence of MoO₃ and a cycloalkane.

In general, component f) can also be represented, for example, by acompound of the formula VIII1, VIII2 or VIII3, the hydrogens on thenitrogen atoms of the 2,2,6,6-tetramethyl-4-piperidyl radicals beingreplaced by groups --OR₂₀. It can also be present as a mixture of thesethree compounds.

The product described as component f), for example, is also obtainableby reacting a product, obtained by reaction between a polyamine of theformula VIIIa and cyanuric chloride, with a compound of the formulaVIIId ##STR23## in which n₄ ', n₄ " and n₄ '" independently of oneanother are a number from 2 to 12,

R₁₉ is hydrogen, C₁ -C₁₂ alkyl, C₅ -C₁₂ cycloalkyl, phenyl or C₇ -C₉phenylalkyl, and

R₂₀ is as defined for R₁.

The reaction can take place, for example, in analogy to the preparationprocess described in U.S. Pat. No. 4,477,615.

As component a), ®TINUVIN 123 is employed with particular preference.Preferred starting products are also, for the preparation of a compoundof component a), ®MARK LA 57 or ®DASTIB 845, for the preparation of acompound of component b) a precursor of ®CHIMASSORB 119 (unsubstitutednitrogen in the 2,2,6,6-tetramethyl-4-piperidyl groups), for thepreparation of a compound of component d) ®CHIMASSORB 944, ®CYASORB UV3346 or ®DASTIB 1082, for the preparation of a compound of component e)® UVASIL 299 or ®UVASIL 125, for the preparation of a compound ofcomponent f) ®UVASORB HA 88, for the preparation of a compound ofcomponent g) ®UVINUL 5050 H, ®LICHTSCHUTZSTOFF UV 31 or ®LUCHEM HA-B 18,for the preparation of a compound of component h) ®LICHTSCHUTZMITFELS95, for the preparation of a compound of component i) ®HOSTAVIN N 30,for the preparation of a compound of component j) ®HOSTAVIN N20 or®SANDUVOR 3050 and for the preparation of a compound of component k)®MARK LA 68.

The definition of the terminal groups which saturate the free valencesin the compounds of the formulae VI, VII, VIII-1, VIII2, VIII3, IX, XIand XIII depend on the processes used for their preparation. Theterminal groups can also be modified after the preparation of thecompounds.

If the compounds of the formula VI are prepared by reacting a compoundof the formula ##STR24## in which X is for example halogen, especiallychlorine, and R₁₄ and R₁₅ are as defined above, with a compound of theformula ##STR25## in which R₁₁, R₁₂ and R₁₃ are as defined above, thenthe terminal group bonded to the diamino radical is hydrogen or##STR26## and the terminal group bonded to the triazine radical is X or##STR27##

If X is a halogen it is advantageous to replace it, for example, by --OHor an amino group when the reaction is complete. Examples of aminogroups which may be mentioned are pyrrolidin-1-yl, morpholino, --NH₂,--N(C₁ -C₈ alkyl)₂ and --NR(C₁ -C₈ alkyl), in which R is hydrogen or agroup of the formula IV.

In the compounds of the formula VII, the terminal group bonded to thesilicon atom can, for example, be (R₁₆)₃ Si--O-- and the end groupbonded to the oxygen atom can, for example, be --Si(R₁₆)₃.

The compounds of the formula VII can also exist as cyclic compounds ifn₃ is a number from 3 to 10; in other words, the free valences depictedin the structural formulae in that case form a direct bond.

In the compounds of the formula VIII-1, VIII2 and VIII3 the terminalgroup bonded to the triazine radical is, for example, Cl or a group##STR28## and the terminal group bonded to the amino radical is, forexample, hydrogen or a group ##STR29##

In the compounds of the formula IX the terminal group bonded to the2,5-dioxopyrrolidine ring is, for example, hydrogen and the terminalgroup bonded to the radical --C(R₂₇)(R₂₈)-- is, for example, ##STR30##

In the compounds of the formula XI the terminal group bonded to thedimethylene radical can, for example, be --OH and the terminal groupbonded to the oxygen can, for example, be hydrogen. The terminal groupscan also be polyether radicals. In the compounds of the formula XIII theterminal group bonded to the carbonyl radical is, for example, ##STR31##and the terminal group bonded to the oxygen radical is, for example,##STR32## A preferred stabilizer mixture is one in which R₁, R₉, R₁₀,R₁₈, R₂₀, R₂₂, R₃₀, R₃₁, R₃₅ and R₄₁ independently of one another are C₁-C₁₂ alkyl, C₅ -C₈ cycloalkyl or methyl-substituted C₅ -C₈ cycloalkyl.

Preference is likewise given to a stabilizer mixture in which R₁, R₉,R₁₀, R₁₈, R₂₀, R₂₂, R₃₀, R₃₁, R₃₅ and R₄₁ independently of one anotherare methyl, octyl or cyclohexyl.

The following stabilizer mixtures may be mentioned as examples:

1. Stabilizer mixture comprising at least one compound of component a)and at least one compound of component b), c), d), e), f), g), h), i),j), k) or l),

2. Stabilizer mixture comprising at least one compound of component b)and at least one compound of component c), d), e), f), g), h), i), j),k) or l),

3. Stabilizer mixture comprising at least one compound of component c)and at least one compound of component d), e), f), g), h), i), j), k) orl),

4. Stabilizer mixture comprising at least one compound of component d)and at least one compound of component e), f), g), h), i), j), k) or l),

5. Stabilizer mixture comprising at least one compound of component e)and at least one compound of component f), g), h), i), j), k) or l),

6. Stabilizer mixture comprising at least one compound of component f)and at least one compound of component g), h), i), j), k) or l),

7. Stabilizer mixture comprising at least one compound of component g)and at least one compound of component h), i), j), k) or l),

8. Stabilizer mixture comprising at least one compound of component h)and at least one compound of component i), j), k) or l),

9. Stabilizer mixture comprising at least one compound of component i)and at least one compound of component j), k) or l),

10. Stabilizer mixture comprising at least one compound of component j)and at least one compound of component k) or l),

11. Stabilizer mixture comprising at least one compound of component k)and at least one compound of component l),

12. Stabilizer mixture comprising at least two different compounds ofcomponent a),

13. Stabilizer mixture comprising at least two different compounds ofcomponent b),

14. Stabilizer mixture comprising at least two different compounds ofcomponent c),

15. Stabilizer mixture comprising at least two different compounds ofcomponent d),

16. Stabilizer mixture comprising at least two different compounds ofcomponent e),

17. Stabilizer mixture comprising at least two different compounds ofcomponent f),

18. Stabilizer mixture comprising at least two different compounds ofcomponent g),

19. Stabilizer mixture comprising at least two different compounds ofcomponent h),

20. Stabilizer mixture comprising at least two different compounds ofcomponent i),

21. Stabilizer mixture comprising at least two different compounds ofcomponent j),

22. Stabilizer mixture comprising at least two different compounds ofcomponent k),

23. Stabilizer mixture comprising at least two different compounds ofcomponent 1).

The following stabilizer mixtures are preferred:

A. Stabilizer mixture comprising at least one compound of component a)and at least one compound of component b), c), d), e), f), g), h), i),j), k) or l),

B. Stabilizer mixture comprising at least one compound of component a)and at least one compound of component b), c), d), e), f), g), h) or j),

C. Stabilizer mixture comprising at least one compound of component b)and at least one compound of component d), e), f), g) or k) and

D. Stabilizer mixture comprising at least one compound of component c)and at least one compound of component a), b), d), e), f), g), h) or j).

Also preferred is a stabilizer mixture

in which n₁ is 1, 2 or 4,

if n₁ is 1, R₂ is C₁₀ -C₂₀ alkyl,

if n₁ is 2, R₂ is C₆ -C₁₀ alkylene, and

if n₁ is 4, R₂ is butanetetrayl;

R₃ and R₇ independently of one another are hydrogen or C₁ -C₄ alkyl,

R₄, R₅ and R₆ independently of one another are C₂ -C₆ alkylene,

R₈ is hydrogen, C₁ -C₆ alkyl, C₅ -C₈ cycloalkyl, methyl-substituted C₅-C₈ cycloalkyl, phenyl, C₇ -C₉ phenylalkyl or a group of the formula IV;

R₁₁, R₁₃, R₁₄ and R₁₅ independently of one another are hydrogen, C₁ -C₈alkyl, C₅ -C₈ cycloalkyl, methyl-substituted C₅ -C₈ cycloalkyl, phenyl,C₇ -C₉ phenylalkyl or a group of the formula IV, or

the radicals R₁₄ and R₁₅, together with the nitrogen atom to which theyare attached, form a 6-membered heterocyclic ring,

R₁₂ is C₂ -C₁₀ alkylene, and

n₂ is a number from 2 to 25;

R₁₆ is C₁ -C₄ alkyl, C₅ -C₈ cycloalkyl or phenyl,

R₁₇ is C₃ -C₆ alkylene, and

n₃ is a number from 1 to 25;

n₄ ', n₄ " and n₄ '" independently of one another are a number from 2 to4, and R₁₉ is C₁ -C₄ alkyl;

R₂₁ and R₂₆ independently of one another are a direct bond or a group--N(Y₁)--CO--Y₂ --CO--N(Y₃)--,

Y₁ and Y₃ independently of one another are hydrogen or C₁ -C₄ alkyl,

Y₂ is a direct bond,

R₂₃ and R₂₇ are C₁ -C₂₅ alkyl or phenyl,

R₂₄ and R₂₈ are hydrogen or C₁ -C₄ alkyl,

R₂₅ is C₁ -C₂₅ alkyl or a group of the formula IV, and

n₅ is a number from 1 to 25;

R₂₉ is C₈ -C₁₅ alkyl;

n₆ is a number from 2 to 25;

R₃₂ and R₃₃ together form C₈ -C₁₄ alkylene,

R₃₄ is hydrogen or a group --Z₁ --COO--Z₂, Z₁ is C₂ -C₆ alkylene and Z₂is C₈ -C₁₅ alkyl;

R₃₆, R₃₈, R₃₉ and R₄₀ independently of one another are C₁ -C₄ alkylene,

R₃₇ is a direct bond, and

n₇ is a number from 1 to 25.

A particularly preferred stabilizer mixture is one in which

component a) is at least one compound of the formula a-I-1, a-I-2 ora-I-3, ##STR33## in which R₁ is methyl, octyl or cyclohexyl; componentb) is at least one compound of the formula b-II, ##STR34## in which R₉is as defined for R₁ ; component c) is at least one compound of theformula c-V, ##STR35## in which R₉ is as defined above; component d) isat least one compound of the formula d-VI-1, d-VI-2 or d-VI-3, ##STR36##in which R₁₀ is as defined for R₁ and n₂ is a number from 2 to 25;

component e) is at least one compound of the formula e-VII, ##STR37## inwhich R₁₈ is as defined for R₁ and n₃ is a number from 1 to 25;

component f) is a product obtainable by reacting a product, obtained byreaction between a polyamine of the formula

    H.sub.2 N--(CH.sub.2).sub.3 --NH (CH.sub.2).sub.2 --NH--(CH.sub.2).sub.3 --NH.sub.2

and cyanuric chloride, with a compound of the formula ##STR38## to forma triazine derivative which contains 2,2,6,6-tetramethyl-4-piperidylgroups, and then reacting the 2,2,6,6-tetramethyl-4-piperidyl groupspresent in the triazine derivative to form groups of the formula##STR39## in which R₂₀ is as defined for R₁ ; component g) is at leastone compound of the formula g-IX-1, g-IX-2 or g-IX-3, ##STR40## in whichR₁₀ and R₂₂ are as defined for R₁ and n₅ is a number from 1 to 25;

component h) is at least one compound of the formula h-X ##STR41## inwhich R₃₀ is as defined for R₁ ; component i) is at least one compoundof the formula XI in which R₃₁ is as defined for R₁ and n₆ is a numberfrom 2 to 25;

component j) is at least one compound of the formula j-XII1 or j-XII2,##STR42## in which R₃₅ is as defined for R₁ ; component k) is at leastone compound of the formula k-XIII, ##STR43## in which R₄₁ is as definedfor R₁ and n₇ is a number from 1 to 25;

component 1) is at least one compound of the formula 1-XIV, ##STR44## inwhich R₉ is as defined for R₁.

The following stabilizer systems are of particular interest:

a-1) Stabilizer mixture comprising at least one compound of the formulaa-I-1 and at least one compound of the formula d-VI-1 in which R₁ andR₁₀ independently of one another are, for example, methyl, octyl orcyclohexyl and R₁ is preferably octyl,

a-2) Stabilizer mixture comprising at least one compound of the formulaa-I-1 and at least one compound of the formula b-II in which R₁ and R₉independently of one another are, for example, methyl, octyl orcyclohexyl and R₁ is preferably octyl, and R₉ is preferably cyclohexyl,

a-3) Stabilizer mixture comprising at least one compound of the formulaa-I-1 and at least one compound characterized by component f), where R₁and R₂₀ independently of one another are, for example, methyl, octyl orcyclohexyl and R₁ is preferably octyl,

a-4) Stabilizer mixture comprising at least one compound of the formulaa-I-1 and at least one compound of the formula d-VI-2 in which R₁ andR₁₀ independently of one another are, for example, methyl, octyl orcyclohexyl and R₁ is preferably octyl,

a-5) Stabilizer mixture comprising at least one compound of the formulaa-I-1 and at least one compound of the formula c-V in which R₁ and R₉independently of one another are, for example, methyl, octyl orcyclohexyl and R₁ is preferably octyl and R₉ is preferably methyl orcyclohexyl,

a-6) Stabilizer mixture comprising at least one compound of the formulaa-I-1 and at least one compound of the formula e-VII in which R₁ and R₁₈independently of one another are, for example, methyl, octyl orcyclohexyl and R₁ is preferably octyl,

a-7) Stabilizer mixture comprising at least one compound of the formulaa-I-1 and at least one compound of the formula g-IX-1 in which R₁ andR₂₂ independently of one another are, for example, methyl, octyl orcyclohexyl and R₁ is preferably octyl,

b-1) Stabilizer mixture comprising at least one compound of the formulac-V and at least one compound of the formula d-VI-1 in which R₉ and R₁₀independently of one another are, for example, methyl, octyl orcyclohexyl and R₉ is preferably methyl or cyclohexyl,

b-2) Stabilizer mixture comprising at least one compound of the formulac-V and at least one compound of the formula b-II in which R₉ is, forexample, methyl, octyl or cyclohexyl and in the formula c-V ispreferably methyl or cyclohexyl and in the formula b-II is preferablycyclohexyl,

b-3) Stabilizer mixture comprising at least one compound of the formulac-V and at least one compound characterized by component f), in which R₉and R₂₀ independently of one another are, for example, methyl, octyl orcyclohexyl and R₉ is preferably methyl or cyclohexyl,

b-4) Stabilizer mixture comprising at least one compound of the formulac-V and at least one compound of the formula d-VI-2 in which R₉ and R₁₀independently of one another are, for example, methyl, octyl orcyclohexyl and R₉ is preferably methyl or cyclohexyl,

b-5) Stabilizer mixture comprising at least one compound of the formulac-V and at least one compound of the formula e-VII in which R₉ and R₁₈independently of one another are, for example, methyl, octyl orcyclohexyl and R₉ is preferably methyl or cyclohexyl,

b-6) Stabilizer mixture comprising at least one compound of the formulac-V and at least one compound of the formula g-IX-1 in which R₉ and R₂₂independently of one another are, for example, methyl, octyl orcyclohexyl and R₉ is preferably methyl or cyclohexyl,

c-1) Stabilizer mixture comprising at least one compound of the formulab-II and at least one compound of the formula a-I-3 in which R₁ and R₉independently of one another are, for example, methyl, octyl orcyclohexyl and R₉ is preferably cyclohexyl,

c-2) Stabilizer mixture comprising at least one compound of the formulab-II and at least one compound of the formula j-XII1 in which R₉ and R₃₅independently of one another are, for example, methyl, octyl orcyclohexyl and R₉ is preferably cyclohexyl,

c-3) Stabilizer mixture comprising at least one compound of the formulab-II and at least one compound of the formula h-X in which R₉ and R₃₀independently of one another are, for example, methyl, octyl orcyclohexyl and R₉ is preferably cyclohexyl, and

c-4) Stabilizer mixture comprising at least one compound of the formulab-II and at least one compound of the formula a-I-2 in which R₁ and R₉independently of one another are, for example, methyl, octyl orcyclohexyl and R₉ is preferably cyclohexyl.

In the abovementioned stabilizer systems the two compounds areparticularly preferably present in a weight ratio of from 1:4 to 4:1.

The stabilizer mixture according to the invention is suitable forstabilizing organic materials against thermal, oxidative orlight-induced degradation. Examples of such materials are:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene orpolybutadiene, as well as polymers of cycloolefins, for instance ofcyclopentene or norbornene, polyethylene (which optionally can becrosslinked), for example high density polyethylene (HDPE), high densityand high molecular weight polyethylene (HDPE-HMW), high density andultrahigh molecular weight polyethylene (HDPE-UHMW), medium densitypolyethylene (MDPE), low density polyethylene (LDPE), linear low densitypolyethylene (LLDPE), branched low density polyethylene (BLDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

a) radical polymerisation (normally under high pressure and at elevatedtemperature).

b) catalytic polymerisation using a catalyst that normally contains oneor more than one metal of groups IVb, Vb, VIb or VIII of the PeriodicTable. These metals usually have one or more than one ligand, typicallyoxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenylsand/or aryls that may be either π- or σ-coordinated. These metalcomplexes may be in the free form or fixed on substrates, typically onactivated magnesium chloride, titanium(III) chloride, alumina or siliconoxide. These catalysts may be soluble or insoluble in the polymerisationmedium. The catalysts can be used by themselves in the polymerisation orfurther activators may be used, typically metal alkyls, metal hydrides,metal alkyl halides, metal alkyl oxides or metal alkyloxanes, saidmetals being elements of groups Ia, IIa and/or IIIa of the PeriodicTable. The activators may be modified conveniently with further ester,ether, amine or silyl ether groups. These catalyst systems are usuallytermed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont),metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/-isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

4. Hydrocarbon resins (for example C₅ -C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with dienes or acrylicderivatives, for example styrene/butadiene, styrene/acrylonitrile,styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate,styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride,styrene/acrylonitrile/methyl acrylate; mixtures of high impact strengthof styrene copolymers and another polymer, for example a polyacrylate, adiene polymer or an ethylene/-propylene/diene terpolymer; and blockcopolymers of styrene such as styrene/butadiene/-styrene,styrene/isoprene/styrene, styrene/ethylene/butylene/styrene orstyrene/ethylene/-propylene/ styrene.

7. Graft copolymers of styrene or α-methylstyrene, for example styreneon polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene andalkyl acrylates or methacrylates on polybutadiene; styrene andacrylonitrile on ethylene/propylene/diene terpolymers; styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 6), for example the copolymermixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated and brominated copolymer of isobutylene-isoprene(halobutyl rubber), chlorinated or sulfochlorinated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride, polyvinylidene fluoride, as well as copolymersthereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/ butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyetherimids,polyesterimids, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates,as well as block copolyether esters derived from hydroxyl-terminatedpolyethers; and also polyesters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, isocyanates, isocyanurates,polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidylethers of bisphenol A and bisphenol F, which are crosslinked withcustomary hardeners such as anhydrides or amines, with or withoutaccelerators.

27. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, for example cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.

28. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

29. Naturally occurring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, typically those used as spinning compositions, aswell as aqueous emulsions of such materials.

30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

The invention therefore additionally relates to a composition comprisingan organic material which is sensitive to oxidative, thermal orlight-induced degradation and a stabilizer mixture according to theinvention.

The organic material is preferably a synthetic polymer, especially onefrom the groups indicated above. Polyolefins are preferred, andparticular preference is given to polyethylene, polypropylene andcopolymers thereof.

The two compounds of the stabilizer system according to the inventioncan be added to the material to be stabilized individually or mixed withone another. In this context the overall quantity of the compounds canbe from 0.01 to 5%, preferably from 0.05 to 3%, in particular from 0.05to 2% or from 0.05 to 1%, based on the overall weight of the material tobe stabilized.

The weight ratio of the two compounds is preferably from 10:1 to 1:10,for example from 1:5 to 5:1 or from 1:4 to 4:1.

The stabilizer mixture according to the invention or the individualcompounds can be incorporated into the organic material by knownmethods, for example before or during shaping or by applying thedissolved or dispersed compounds to the organic material, if desiredwith subsequent evaporation of the solvent. The individual compounds ofthe stabilizer mixture according to the invention can be added to thematerial to be stabilized in the form of a powder, as granules or elseas a masterbatch, which contains these components in a concentration,for example, of from 2.5 to 25% by weight.

If desired, the compounds of the stabilizer system according to theinvention can be mixed with one another in the melt (melt blending)before incorporation.

The stabilizer system according to the invention or its compounds can beadded before or during polymerization or prior to crosslinking.

The materials stabilized in this way can be employed in a wide varietyof forms, for example as films, fibres, tapes, moulding compositions orprofiles or as binders for coatings, adhesives or putties.

The stabilized organic materials of the invention can additionallycomprise various conventional additives, for example:

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example,2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol,2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol,2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-do-decylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol,2,5-di-tert-butylhydroquinone,-2,5-di-tert-amylhydroquinone,2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone,2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyphenyl stearate,bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (Vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol),4,4'-thiobis(6-tert-butyl-3-methylphenol),4,4'-thiobis(6-tert-butyl-2-methylphenol),4,4'-thiobis-(3,6-di-sec-amylphenol),4,4'-bis-(2,6-dimethyl-4-hydroxyphenyl) disulfide.

1.6. Alkylidenebisphenols, for example2,2'-methylenebis(6-tert-butyl-4-methylphenol),2,2'-methylenebis(6-tert-butyl-4-ethylphenol),2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol],2,2'-methylenebis(4-methyl-6-cyclohexylphenol),2,2'-methylenebis(6-nonyl-4-methylphenol),2,2'-methylenebis(4,6-di-tert-butylphenol),2,2'-ethylidenebis(4,6-di-tert-butylphenol),2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2'-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2'-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4'-methylenebis(2,6-di-tert-butylphenol),4,4'-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis]3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy2-methylphenyl)pentane.

1.7. O-, N- and S-benzyl compounds, for example3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine Compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy3-methylbenzylphosphonate, the calciumsalt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethyloipropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine,N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine,N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.

1.18. Ascorbic acid (vitamin C)

1.19. Aminic antioxidants, for exampleN,N'-di-isopropyl-p-phenylenediamine,N,N'-di-sec-butyl-p-phenylenediamine,N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N'-bis(1-methylheptyl)-p-phenylenediamine,N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine,N,N'-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N'-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine,N-cyclohexyl-N'-phenyl-p-phenylenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylamino-phenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino) propane,(o-tolyl)biguanide, Bis[4-(1', 3'-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- und dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- und dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- und dialkylatedtert-octylphenothiazines, N-allylphenothiazin,N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV Absorbers and Light Stabilisers

2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example2-(2'-hydroxy-5'-methylphenyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole,2-(5'2'-hydroxyphenyl)benzotriazole,2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chloro-benzotriazole,2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole,2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole,2-(3'-,5'-bis-(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole,mixture of2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole,2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, and2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];the transesterification product of2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300; [R--CH₂ CH₂ --COO(CH₂) ₃ ]₂ --, whereR=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl.

2.2. 2-Hydroxybenzophenone, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxyand 2'-hydroxy-4,4'-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, as forexample 4-tertbutylphenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol,benzoyl resorcinol, 2,4-di-tertbutylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano-β-methyl-p-methoxy-cinnamate, butylα-cyano-β-methyl-p-methoxy-cinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, the condensate ofN,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate,1,1'-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dion,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, the condensate ofN,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, the condensateof2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,3-dodecl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product ofN,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-61]);N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid,2-undecyl-7,7,9,9-tetramethyl1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane und epichlorohydrin.

2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide,2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide,2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide,N,N'-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide and mixtures of ortho- andpara-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine.

3. Metal deactivators, for example N,N'-diphenyloxamide,N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl) hydrazine,N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyloyl)oxalyldihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite.

5. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone,N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone,N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridecyl-nitrone,N-hexadecyl-alpha-pentadecyl-nitrone,N-octadecyl-alpha-heptadecyl-nitrone,N-hexadecyl-alpha-heptadecyl-nitrone,N-ocatadecyl-alpha-pentadecyl-nitrone,N-heptadecyl-alpha-heptadecyl-nitrone,N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived fromN,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

7. Thiosynergists, for example, dilauryl thiodipropionate or distearylthiodipropionate.

8. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

9. Polyamide stabilisers, for example, copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or tinpyrocatecholate.

11. Nucleating agents, for example, inorganic substances such as talcum,metal oxides such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals; organiccompounds such as mono- or polycarboxylic acids and the salts thereof,e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate; polymeric compounds such as ioniccopolymers ("ionomers").

12. Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica,barium sulfate, metal oxides and hydroxides, carbon black, graphite,wood flour and flours or fibers of other natural products, syntheticfibers.

13. Other additives, for example, plasticisers, lubricants, emulsifiers,pigments, rheology additives, catalysts, flow-control agents, opticalbrighteners, flameproofing agents, antistatic agents and blowing agents.

14. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863, U.S. Pat. No. 4,338,244, U.S. Pat. No. 5,175,312,U.S. Pat. No. 5,216,052, U.S. Pat. No. 5,252,643, DE-A-4,316,611,DE-A-4,316,622, DE-A-4,316,876, EP-A-0 589 839 or EP-A-0 591 102 or3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]-phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

The weight ratio of stabilizer mixture according to the invention to theconventional additives can, for example, be from 1:0.5 to 1:5.

The invention also relates to the use of the stabilizer mixtureaccording to the invention for stabilizing organic material againstoxidative, thermal or light-induced degradation.

The organic materials stabilized by means of the stabilizer systemaccording to the invention are distinguished not only by significantlyimproved light stability but also, in some cases, by improved thermalstability.

The examples which follow illustrate the invention in more detail. Allpercentages are by weight unless specified otherwise.

Example A

Preparation of the compound of the formula ##STR45##

A solution of 23.6 g (0.098 mol) of4-n-butylamino-1-methoxy-2,2,6,6-tetramethylpiperidine in 25 ml ofxylene is added dropwise to a solution of 4.09 g (0.0217 mol) ofcyanuric chloride in 50 ml of xylene and 6.2 g (0.098 mol) of KOH inpowder form. The reaction mixture is heated at reflux for 23 hours. Thesolids are then removed by filtration and the filtrate is concentratedunder reduced pressure. The crude product obtained is purified bycrystallization (ethanol) to give 14.3 g (82% of theory) of the productindicated above as a white powder. The melting point is 151-153° C.

Elemental analysis for C₄₅ H₈₇ N₉ O₃ Calculated: C, 67.4; H, 10.9; N,15.7 Found: C, 67.4; H, 11.3; N, 15.7

Example B

Preparation of the compound of the formula ##STR46##

0.5 g of MoO₃ is added to a solution of 24.0 g of the compound of theformula ##STR47## in 200 ml of cyclohexane. The solution is heated underreflux, and 20 ml of tert-butyl hydroperoxide (90%) are added over thecourse of 15 minutes. The reaction mixture is heated under reflux for 12hours, then the catalyst is removed by filtration and a further 0.5 g ofMoO₃ is added to the filtrate, followed by 20 ml of 90% tert-butylhydroperoxide. After heating under reflux for 12 hours more, the redcolour has disappeared. The reaction mixture is washed with 5% aqueousNa₂ SO₃ solution until excess hydroperoxide is no longer present. Thereaction solution is washed with water and salt solution, dried overMgSO₄ and evaporated to give 15 g of the compound indicated above as aclear viscous resin without crystals. The NMR and MS data agree with thestructure indicated.

Example C

Preparation of the compound of the formula ##STR48##

Preparation takes place in analogy to the process described in ExampleB, using 31.87 g of the compound of the formula ##STR49##

1.0 g of MoO₃ and 40 ml of 90% tert-butyl hydroperoxide in 600 ml ofcyclohexane, to give 22.2 g of the compound indicated above as a white,vitreous solid. The melting point is 135° C. The NMR and MS data agreewith the structure indicated.

Example D

Preparation of the compound of the formula ##STR50##

Preparation takes place in analogy to the process described in ExampleB, using 25.1 g of the compound of the formula ##STR51##

2.0 g of MoO₃ and 25 ml of 90% tert-butyl hydroperoxide in 500 ml ofcyclohexane, to give 36.5 g of the compound indicated above as a paleyellow, vitreous solid. The melting point is 105-125° C. The NMR and MSdata agree with the structure indicated.

Example E

Preparation takes place in analogy to the process described in ExampleB, using 25.8 g of ®UVASORB HA 88 [a compound obtainable by reacting aproduct, obtained by reaction between a polyamine of the formula

    H.sub.2 N--(CH.sub.2).sub.3 --NH--(CH.sub.2).sub.2 --NH--(CH.sub.2)--NH.sub.2

and cyanuric chloride, with a compound of the formula ##STR52##

2.0 g of MoO₃ and 40 ml of 70% tert-butyl hydroperoxide in 500 ml ofcyclohexane, to give 47.7 g of a corresponding compound which nowcontains, instead of 2,2,6,6-tetramethyl-4-piperidyl groups,1-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl groups. The compound ispresent as a pale yellow resin with a few white crystals. The meltingpoint is 135-145° C. Sintering occurs at 112° C. The NMR and MS dataagree with the structure indicated.

Example F

Preparation of the compound of the formula ##STR53##

11.0 g (14.5 mmol based on the repeating unit) of the compound of theformula ##STR54## are dissolved in 200 ml of cyclohexane. 0.1 g of MoO₃is added and the mixture is heated to reflux. 10 g (77.5 mmol) of a 70%(% by weight/weight) aqueous tert-butyl hydroperoxide solution are addedslowly dropwise at 80° C. The water/tert-butanol mixture which formsduring the reaction is distilled off azeotropically. The mixture is thenheated at reflux for 14 hours, cooled to 20-30° C., added to powderedcoal and filtered. The solution is washed twice with 10% (% byweight/weight) aqueous Na₂ SO₃ and with water. The organic phase isdried over Na₂ SO₄ and filtered and the filtrate is evaporated at 80°C./24 mbar. The residue obtained is a white powder with a melting pointof 104-108° C. The NMR (¹ H, ¹³ C) analysis agrees with the structureindicated above.

Example G

Preparation of the compound of the formula ##STR55##

Preparation takes place in analogy to the process described in ExampleF. 11 g (10.3 mmol) based on the repeating unit) of the compound of theformula ##STR56## are reacted with 10 g of a 10% (% by weight/weight)tert-butyl hydroperoxide solution in cyclohexane in the presence of 0.1g of MoO₃, to give, after evaporation, a white solid with a meltingpoint of 135-139° C. NMR (¹ H, ¹³ C) analysis agrees with the structureindicated above.

Example H

Preparation of the compound of the formula ##STR57##

Preparation takes place in analogy to the process described in ExampleF. 19 g (30.8 mmol, based on the repeating unit) of the compound of theformula ##STR58## are reacted with 6.6 g of a 70% (% by weight/weight)aqueous tert-butyl hydroperoxide solution in cyclohexane in the presenceof 0.5 g of MoO₃, giving, after evaporation, a yellow solid with amelting point of 80-87° C. The NMR (¹ H, ¹³ C) analysis agrees with thestructure indicated above.

Example I

Preparation of the compound of the formula ##STR59##

Preparation takes place in analogy to the process described in ExampleF. 30 g (39.2 mmol) based on the repeating unit) of the compound of theformula ##STR60## are reacted with 15.2 g of a 70% (% by weight/weight)aqueous tert-butyl hydroperoxide solution in cyclohexane in the presenceof 0.8 g of MoO₃, to give, after evaporation, a yellow solid with amelting point of 72-77° C. The NMR (¹ H, ¹³ C) analysis agrees with thestructure indicated above.

The light stabilizers used in Examples 1 to 3

(The mean degree of polymerization is indicated in each case.)

Light stabilizer a-1 (U.S. Pat. No. 5,204,473, Example 58): ##STR61##

Light stabilizer a-2 (U.S. Pat. No. 5,204,473, Example 4): ##STR62##

Light stabilizer b-1 (U.S. Pat. No. 5,204,473, Example 62): ##STR63##

Light stabilizer c-1 (Example A): ##STR64##

Light stabilizer c-2 (U.S. Pat. No. 5,204,473, Example 63): ##STR65##

Light stabilizer d-1 (Example D): ##STR66##

Light stabilizer d-2 (Example C): ##STR67##

Light stabilizer e-1 (Example B): ##STR68##

Light stabilizer f-1 (Example E):

®UVASORB HA 88 containing, instead of 2,2,6,6-tetramethyl-4-piperidylgroups, 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl groups.

Light stabilizer g-2 (Example G): ##STR69##

Light stabilizer k-1 (Example F): ##STR70##

Example 1

Light stabilization in polypropylene films.

100 parts of polypropylene block copolymer powder are homogenized with0.05 part of pentaerythrityltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.10 part oftris[2,4-di-tert-butylphenyl] phosphite, 0.1 part of calcium stearateand the quantities of light stabilizers indicated in Table 1 in aBrabender plastograph at 200° C. for 10 minutes. The composition thusobtained is removed from the compounder as rapidly as possible andpressed in a toggle press to give a sheet with a thickness of 2-3 mm. Apiece of the resultant green moulding is cut out and pressed between twohigh-gloss hard aluminium foils for 6 minutes at 260° C. using alaboratory hydraulic press to give a film with a thickness of 0.5 mm,which is immediately cooled in a water-cooled press. Sections eachmeasuring 55 mm×9 mm are then punched out of this 0.5 mm film and areexposed in a SEPAP 12.24. These test specimens are removed from theexposure apparatus at regular intervals and tested for their carbonylcontent in an IR spectrometer. The increase in the carbonyl absorbanceon exposure is a measure of the photooxidative degradation of thepolymer and is known from experience to be associated with adeterioration in the mechanical properties. The measure of thestabilizing effect is therefore the time (T₀.2 measured) until acarbonyl absorbance of 0.2 is reached. The results are summarized inTable 1.

The synergistic effect is determined by comparing the calculated withthe measured T₀.2 values. The T₀.2 values are calculated according tothe law of additivity (B. Ranby and J. F. Rabek, Photodegradation,Photo-oxidation and Photostabilization of Polymers, Principles andApplications, a Wiley-Interscience Publication, 1975, pages 418-422) inaccordance with the following equation: ##EQU1##

The mixture in question has a synergistic effect if T₀.2 measured isgreater than T₀.2 calculated.

T₀.2 calculated is likewise indicated in Table 1.

                  TABLE 1                                                         ______________________________________                                        Light stabilization in polypropylene films.                                                      T.sub.0.2 measured                                                                      T.sub.0.2 calculated                               Light stabilizer in hours in hours                                          ______________________________________                                        None (control)  58                                                              0.1% a-1 450                                                                  0.1% b-1 360                                                                  0.1% c-2 575                                                                  0.05% a-1 and 540 405                                                         0.05% b-1                                                                     0.05% a-1 and 615 512                                                         0.05% c-2                                                                   ______________________________________                                    

Example 2

Light stabilization in polypropylene block copolymer films.

100 parts of polypropylene block copolymer powder are homogenized with0.05 part of pentaerythrityltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.10 part oftris[2,4-di-tert-butylphenyl]phosphite, 0.1 part of calcium stearate andthe parts of light stabilizer indicated in Tables 2a and 2b for 10minutes at 200° C. in a Brabender plastograph. The composition thusobtained is removed from the compounder as rapidly as possible andpressed in a toggle press to give a sheet with a thickness of 2-3 mm. Apiece of the resultant green moulding is cut out and pressed between twohigh-gloss hard aluminium foils for 6 minutes at 260° C. by means of alaboratory hydraulic press to give a sheet with a thickness of 0.5 mm,which is immediately cooled in a water-cooled press. Pieces eachmeasuring 60 mm×25 mm are then punched out of this 0.5 mm sheet andexposed to light in a WEATHER-OMETER Ci 65 (black standard temperature63+/-2° C., no exposure to rainwater). These test specimens are removedfrom the exposure apparatus at regular intervals and tested for theircarbonyl content in an IR spectrometer. The increase in the carbonylabsorbance on exposure is a measure of the photooxidative degradation ofthe polymer and is known from experience to be associated with adeterioration in the mechanical properties.

The time (T₀.2 measured), until a carbonyl absorbance of 0.2 is reachedis indicated in Tables 2a and 2b.

The synergistic effect can be determined by comparing the calculatedwith the measured T₀.2 values, in analogy to Example 1.

                  TABLE 2a                                                        ______________________________________                                        Light stabilization in polypropylene block copolymer films.                                      T.sub.0.2 measured                                                                      T.sub.0.2 calculated                               Light stabilizer in hours in hours                                          ______________________________________                                        none            145                                                             0.1% a-1 1155                                                                 0.1% a-2 2280                                                                 0.1% b-1 1430                                                                 0.1% c-1 2880                                                                 0.1% c-2 1950                                                                 0.05% a-1 and 2020 1292                                                       0.05% b-1                                                                     0.05% a-1 and 2300 2017                                                       0.05% c-1                                                                     0.05% a-1 and 1960 1552                                                       0.05% c-2                                                                     0.05% a-2 and 2420 1855                                                       0.05% b-1                                                                     0.05% b-1 and 2360 2155                                                       0.05% c-1                                                                     0.05% b-1 and 1910 1690                                                       0.05% c-2                                                                     0.05% c-1 and 2480 2415                                                       0.05% c-2                                                                   ______________________________________                                    

                  TABLE 2b                                                        ______________________________________                                        Light stabilization in polypropylene block copolymer films.                                      T.sub.0.2 measured                                                                      T.sub.0.2 calculated                               Light stabilizer in hours in hours                                          ______________________________________                                        none            145                                                             0.2% a-1 2230                                                                 0.2% c-2 3360                                                                 0.10% a-1 and 3020 2795                                                       0.10% c-2                                                                   ______________________________________                                    

In a second series of tests, additional combinations are tested underthe same conditions as above. The results are given in Table 3.

                  TABLE 3                                                         ______________________________________                                        Light stabilization in polypropylene block copolymer films.                                      T.sub.0.2 measured                                                                      T.sub.0.2 calculated                               Light stabilizer in hours in hours                                          ______________________________________                                        none            100                                                             0.2% a-1 2230                                                                 0.2% a-2 4040                                                                 0.2% b-1 1750                                                                 0.2% d-1 1480                                                                 0.2% d-2  480                                                                 0.2% e-1 3180                                                                 0.2% f-1 1560                                                                 0.2% g-2  330                                                                 0.2% k-1 1800                                                                 0.1% a-1 and 2080 1855                                                        0.1% d-1                                                                      0.1% a-1 and 1880 1355                                                        0.1% d-2                                                                      0.1% a-1 and 3180 2705                                                        0.1% e-1                                                                      0.1% a-1 and 2390 1895                                                        0.1% f-1                                                                      0.1% a-1 and 1480 1280                                                        0.1% g-2                                                                      0.1% a-1 and 2350 2015                                                        0.1% k-1                                                                      0.1% a-2 and 3340 2760                                                        0.1% d-1                                                                      0.1% a-2 and 3280 2260                                                        0.1% d-2                                                                      0.1% a-2 and >4319  3610                                                      0.1% e-1                                                                      0.1% a-2 and 3700 2800                                                        0.1% f-1                                                                      0.1% a-2 and 2380 2185                                                        0.1% g-2                                                                      0.1% a-2 and 3020 2920                                                        0.1% k-1                                                                      0.1% b-1 and 1790 1615                                                        0.1% d-1                                                                      0.1% b-1 and 1520 1115                                                        0.1% d-2                                                                      0.1% b-1 and 3350 2465                                                        0.1% e-1                                                                      0.1% b-1 and 2120 1775                                                        0.1% k-1                                                                    ______________________________________                                    

Example 3

Light stabilization in low-density polyethylene films.

100 parts of low-density (density=0.918 g/cm³) polyethylene powder arehomogenized with 0.03 part of octadecyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and with the parts oflight stabilizers indicated in Table 4 in a Brabender plastograph at180° C. for 10 minutes. The composition thus obtained is removed fromthe compounder as rapidly as possible and pressed in a press to give asheet with a thickness of 2-3 mm. A piece of the resultant greenmoulding is cut out and pressed between two high-gloss hard aluminiumfoils for 6 minutes at 170° C. using a laboratory hydraulic press togive a film with a thickness of 0.2 mm, which is immediately cooled in awater-cooled press. Sections each measuring 60 mm×25 mm are then punchedout of this 0.2 mm film and are immersed for 24 hours in a 0.1 N H₂ SO₃solution. This is regarded as a simulation of acid rain. The samples arethen exposed to light in a WEATHER-OMETER Ci 65 (black standardtemperature 63+/-2° C., no simulated rainwater). These samples areremoved from the exposure apparatus at regular intervals and are testedfor their content of vinyl groups in an IR spectrometer. The increase inthe vinyl absorbance (909 cm⁻¹) on exposure is a measure of thephotooxidative degradation of the polymer and is known from experienceto be associated with a deterioration in the mechanical properties.

                  TABLE 4                                                         ______________________________________                                        Light stabilization in low-density polyethylene films.                                        Vinyl abosrbance                                                                            Calculated vinyl                                  Light stabilizer after 4106 hours absorbance                                ______________________________________                                        none        0.125 after 592 hours                                               0.1% a-1 0.037                                                                0.1% a-2 0.023                                                                0.1% b-1 0.046                                                                0.1% d-1 0.100                                                                0.1% d-2 >0.122                                                               0.1% e-1 0.059                                                                0.1% f-1 0.052                                                                0.1% g-2 >0.100                                                               0.1% k-1 0.037                                                                0.05% a-1 and 0.031 >0.068                                                    0.05% d-1                                                                     0.05% a-1 and 0.021 >0.080                                                    0.05% d-2                                                                     0.05% a-1 and 0.000 0.048                                                     0.05% e-1                                                                     0.05% a-1 and 0.025 0.045                                                     0.05% f-1                                                                     0.05% a-1 and 0.024 >0.068                                                    0.05% g-2                                                                     0.05% a-1 and 0.000 0.037                                                     0.05% k-1                                                                     0.05% a-2 and 0.030 >0.040                                                    0.05% d-1                                                                     0.05% a-2 and 0.029 >0.072                                                    0.05% d-2                                                                     0.05% a-2 and 0.023 0.041                                                     0.05% e-1                                                                     0.05% a-2 and 0.023 0.061                                                     0.05% f-1                                                                     0.05% a-2 and 0.028 >0.062                                                    0.05% g-2                                                                     0.05% b-1 and 0.067 0.073                                                     0.05% d-1                                                                     0.05% b-1 and 0.052 >0.084                                                    0.05% d-2                                                                     0.05% b-1 and 0.042 0.052                                                     0.05% e-1                                                                     0.05% b-1 and 0.042 0.049                                                     0.05% f-1                                                                     0.05% b-1 and 0.051 >0.073                                                    0.05% g-2                                                                   ______________________________________                                    

What is claimed is:
 1. A composition comprising(A) an organic materialwhich is sensitive to oxidative, thermal or light-induced degradation,and (B) an effective stabilizing amount of a stabilizer mixturecomprising a component a) and a component b), c), d), e), f), g) or k),wherecomponent a) is at least one compound of the formula a-I-1 ora-I-3, ##STR71## in which R₁ is methyl, octyl or cyclohexyl; componentb) is at least one compound of the formula b-II, ##STR72## in which R₉is as defined for R₁ ; component c) is at least one compound of theformula c-V, ##STR73## in which R₉ is as defined above; component d) isat least one compound of the formula d-VI-1, d-VI-2 or d-VI-3, ##STR74##in which R₁₀ is as defined for R₁ and n₂ is a number from 2 to 25;component e) is at least one compound of the formula e-VII, ##STR75## inwhich R₁₈ is as defined for R₁ and n₃ is a number from 1 to 25;component f) is a product obtainable by reacting a product, obtained byreaction between a polyamine of the formula

    H.sub.2 N--(CH.sub.2).sub.3 --NH--(CH.sub.2).sub.2 --NH--(CH.sub.2).sub.3 --NH.sub.2

and cyanuric chloride, with a compound of the formula ##STR76## to forma triazine derivative which contains 2,2,6,6-tetramethyl-4-piperidylgroups, and then reacting the 2,2,6,6-tetramethyl-4-piperidyl groupspresent in the triazine derivative to form groups of the formula##STR77## in which R₂₀ is as defined for R₁ ; component g) is at leastone compound of the formula g-IX-1 or g-IX-2, ##STR78## in which R₁₀ andR₂₂ are as defined for R₁ and n₅ is a number from 1 to 25; and componentk) is at least one compound of the formula k-XIII, ##STR79## in whichR₄₁ is as defined for R₁ and n₇ is a number from 1 to 25, or aneffective stabilizing amount of a stabilizer mixture comprising acomponent b) and a component c), d), e), f), g) or k), or an effectivestabilizing amount of a stabilizer mixture comprising at least 2different compounds of component c), d), e), f), g) or k).
 2. Acomposition according to claim 1, wherein the organic material is apolyolefin.
 3. A composition according to claim 1, wherein the organicmaterial is polyethylene, polypropylene or a copolymer of polyethyleneor polypropylene.
 4. A composition according to claim 1 wherein thestabilizer mixture comprises at least one compound of component a) andat least one compound of component b), c), d), e), f) or g).